JP2004529202A5 - - Google Patents

Description

The reaction zone is continuously washed with a gas or gas mixture inert under the reaction conditions, such as nitrogen, air, an air-nitrogen mixture or a nitrogen-oxygen mixture, argon, helium, carbon dioxide or carbon monoxide. be able to. This cleaning gas can be used as described in the German patent application DE 101 27 938 A1 having the same filing date as the present application, entitled "Process for the preparation of (meth) acrylates", It is particularly advantageous to conduct along existing heat exchanger surfaces, in particular in the existing pump circuit or natural circuit.

The remaining portion of the condensate can be returned directly, ie without additional purification steps, to the synthesis of lower alkyl (meth) acrylate I, in which the remaining portion of the condensate is ) Acrylic acid can be reacted again to give the starting ester, which is, for example, the German patent application having the same filing date as the present application and having the application date 10277941.8 (publication number DE10127941) , the name "(meta) A) Method for producing acrylic acid ester ". This can advantageously be fed there to a work-up process, in particular an extraction process.

Claims (19)

The following formula:

[Where,
R is H or CH ₃ ,
R ¹ is C ₁ -C ₁₁ -alkyl;
R ² is _C 3 _{-C 12} substituted by ^NR _{3 2} groups - alkyl, - alkyl or _C 2 _{-C 12}
R ³ is C ₁ -C ₆ -alkyl;
In this case, N may form a 5- to 7-membered ring together with R ³ , and R ³ may be the same or different.] (Meth) acrylic acid by subjecting an alcohol R ² OH having at least one more carbon atom than the alcohol component (R ¹ O—) in the (meth) acrylate ester I to a transesterification reaction in the presence of a catalyst or a catalyst mixture In the process for the preparation of ester IV, the lower alkanol R ¹ OH liberated during the transesterification reaction is converted into the lower (meth) acrylate I in one or more columns attached to one or more reactors. Separated together with a portion and fed into the apparatus for the production and / or work-up of (meth) acrylate I without additional purification steps, From the carry-out amount,
First (meth) separating the major amount of the acrylic acid ester I, then catalyst used by distillation to separate (catalyst separation),
Thereafter, the resulting mixture (meth) away min Ri by the distillation component is readily boiling than acrylic acid ester IV (easy boiling product separation), continue (meth) purified by distillation an acrylic acid ester IV ( Rectification)
The method for producing (meth) acrylic acid ester IV, wherein the catalyst separation is carried out at 125 to 160 ° C. (Meth) acrylic acid ester I, n-propanol, isopropanol, allyl alcohol, n-butanol, 1-methylpropanol, 2-methylpropanol, t-butanol, n-pentanol, 1-methylbutanol, 2-methylbutanol , 3-methylbutanol, 2,2-dimethylpropanol, n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 2, 2-dimethylbutanol, 3,3-dimethylbutanol, 1,2-dimethylbutanol, n-heptanol, 1-methylhexanol, 2-methylhexanol, 3-methylhexanol, 4-methylhexanol, 1,2-dimethylpentanol , 1,3-dimethyl Tertanol, 1,1-dimethylpentanol, 1,1,2,2-tetramethylpropanol, benzyl alcohol, n-octanol, 2-ethylhexanol, n-nonanol, 1-methyloctanol, 2-methyloctanol, n- Decanol, n-undecanol, 1-methyldecanol, 2-methyldecanol, n-dodecanol, 2,4-diethyloctanol, cyclopentanol, cyclohexanol, 4-t-butylcyclohexanol, cycloheptanol, cyclododecanol Nol, 2- (dimethylamino) ethanol, 3- (dimethylamino) propanol, 4- (dimethylamino) butanol, 5- (dimethylamino) pentanol, 6- (dimethylamino) hexanol, 8- (dimethylamino) octanol , 0- (dimethylamino) decanol, 12- (dimethylamino) dodecanol, 2- (diethylamino) ethanol, 3- (diethylamino) propanol, 4- (diethylamino) butanol, 5- (diethylamino) pentanol, 6- (diethylamino) Hexanol, 8- (diethylamino) octanol, 10- (diethylamino) decanol, 12- (diethylamino) dodecanol, 2- (di (isopropyl) amino) ethanol, 3- (di (isopropyl) amino) propanol, 4- (di ( (Isopropyl) amino) butanol, 5- (di (isopropyl) amino) pentanol, 6- (di (isopropyl) amino) hexanol, 8- (di (isopropyl) amino) octanol, 10- (di (isopropyl) amino) de Canol, 12- (di (isopropyl) amino) dodecanol, 2- (dibutylamino) ethanol, 3- (dibutylamino) propanol, 4- (dibutylamino) butanol, 5- (dibutylamino) pentanol, 6- (dibutylamino) ) Hexanol, 8- (dibutylamino) octanol, 10- (dibutylamino) decanol, 12- (dibutylamino) dodecanol, 2- (dihexylamino) ethanol, 3- (dihexylamino) propanol, 4- (dihexylamino) butanol 5- (dihexylamino) pentanol, 6- (dihexylamino) hexanol, 8- (dihexylamino) octanol, 10- (dihexylamino) decanol, 12- (dihexylamino) dodecanol, 2- (methylethylamido) ) Ethanol, 2- (methylpropylamino) ethanol, 2- (methylisopropylamino) ethanol, 2- (methylbutylamino) ethanol, 2- (methylhexylamino) ethanol, 2- (methyloctylamino) ethanol, 2- (Ethylpropylamino) ethanol, 2- (ethylisopropylamino) ethanol, 2- (ethylbutylamino) ethanol, 2- (ethylhexylamino) ethanol, 2- (ethyloctylamino) ethanol, 3- (methylethylamino) propanol 3- (methylpropylamino) propanol, 3- (methylisopropylamino) propanol, 3- (methylbutylamino) propanol, 3- (methylhexylamino) propanol, 3- (methyloctylamino) propano 3- (ethylpropylamino) propanol, 3- (ethylisopropylamino) propanol, 3- (ethylbutylamino) propanol, 3- (ethylhexylamino) propanol, 3- (ethyloctylamino) propanol, 4- (methyl Ethyl (amino) butanol, 4- (methylpropylamino) butanol, 4- (methylisopropylamino) butanol, 4- (methylbutylamino) butanol, 4- (methylhexylamino) butanol, 4- (methyloctylamino) butanol, 4- (ethylpropylamino) butanol, 4- (ethylisopropylamino) butanol, 4- (ethylbutylamino) butanol, 4- (ethylhexylamino) butanol, 4- (ethyloctylamino) butanol, 2- (N -Piperidinyl) ethanol, 3- (N-piperidinyl) propanol, 4- (N-piperidinyl) butanol, 5- (N-piperidinyl) pentanol, 6- (N-piperidinyl) hexanol, 8- (N-piperidinyl) octanol 10- (N-piperidinyl) decanol, 12- (N-piperidinyl) dodecanol, 2- (N-pyrrolidinyl) ethanol, 3- (N-pyrrolidinyl) propanol, 4- (N-pyrrolidinyl) butanol, 5- (N -Pyrrolidinyl) pentanol, 6- (N-pyrrolidinyl) hexanol, 8- (N-pyrrolidinyl) octanol, 10- (N-pyrrolidinyl) decanol, 12- (N-pyrrolidinyl) dodecanol, 2- (N-morpholino) ethanol , 3- (N-morpholino) propanol, -(N-morpholino) butanol, 5- (N-morpholino) pentanol, 6- (N-morpholino) hexanol, 8- (N-morpholino) octanol, 10- (N-morpholino) decanol, 12- (N- Morpholino) dodecanol, 2- (N′-methyl-N-piperazinyl) ethanol, 3- (N′-methyl-N-piperazinyl) propanol, 4- (N′-methyl-N-piperazinyl) butanol, 5- (N '-Methyl-N-piperazinyl) pentanol, 6- (N'-methyl-N-piperazinyl) hexanol, 8- (N'-methyl-N-piperazinyl) octanol, 10- (N'-methyl-N-piperazinyl) ) Decanol, 12- (N'-methyl-N-piperazinyl) dodecanol, 2- (N'-ethyl-N-piperazinyl) ethanol 3- (N′-ethyl-N-piperazinyl) propanol, 4- (N′-ethyl-N-piperazinyl) butanol, 5- (N′-ethyl-N-piperazinyl) pentanol, 6- (N′-ethyl) -N-piperazinyl) hexanol, 8- (N'-ethyl-N-piperazinyl) octanol, 10- (N'-ethyl-N-piperazinyl) decanol, 12- (N'-ethyl-N-piperazinyl) dodecanol, 2 -(N'-isopropyl-N-piperazinyl) ethanol, 3- (N'-isopropanol-N-piperazinyl) propanol, 4- (N'-isopropyl-N-piperazinyl) butanol, 5- (N'-isopropyl-N -Piperazinyl) pentanol, 6- (N'-isopropyl-N-piperazinyl) hexanol, 8- (N'-isopropyl-N Piperazinyl) octanol, 10- (N′-isopropyl-N-piperazinyl) decanol, 12- (N′-isopropyl-N-piperazinyl) dodecanol, 3-oxabutanol, 3-oxapentanol, 2,2-dimethyl-4 -Oxapentanol, 3,6-dioxaheptanol, 3,6-dioxaoctanol, 3,6,9-trioxadecanol, 3,6,9-trioxaundecanol, 4-oxapentanol , 4-oxahexanol, 4-oxaheptanol, 4,8-dioxanonanol, 4,8-dioxadecanol, 4,8-dioxaundecanol, 5-oxahexanol or 5,10-di Oxoundecanol, or ethoxylated and / or propoxylated alcohols and mixed ethoxyls / Propoxylated alcohol ^{_{R 5 - (O-CH 2}} -CH 2) x -OH or _{^{R 5 - (O-CH (}} CH 3) -CH 2) x -OH or ^R 5 - (O-CH ₂ —CH (CH ₃ )) _x —OH, wherein R ⁵ represents C ₁ -C ₂₀ -alkyl and x represents an integer from 1 to 20) or ethoxylated and / or propoxylated amino alcohols ^{_{R 3 2 N (-CH 2 CH}} 2 -O) y -H or ^{_{R 3 2 N (-CH (CH}} 3) -CH 2 -O) y -H or ^R _{3 2} N (-CH 2 - CH (CH ₃ ) —O—) _y —H wherein R ³ represents C ₁ -C ₆ -alkyl, wherein N may form a 5- to 7-membered ring with R ³ , and R ³ may be the same or different, and y is selected from 'represents an integer of 1 to 4 With an alcohol R ² OH, in the presence of a catalyst or catalyst mixture by causing transesterification (meth) In the production process of acrylic acid ester IV, is liberated during the transesterification reaction, and methanol, ethanol, n- propanol, The lower alkanol R ¹ OH selected from isopropanol, n-butanol, isobutanol, 2-butanol and t-butanol is separated together with a part of the lower (meth) acrylate I and without additional purification steps The (meth) acrylic acid ester I is fed into an apparatus for the production and / or post-treatment, and from the unreacted product of the transesterification reaction,
First (meth) separating the major amount of the acrylic acid ester I, then catalyst used by distillation to separate (catalyst separation),
Thereafter, the resulting mixture (meth) away min Ri by the distillation component is readily boiling than acrylic acid ester IV (easy boiling product separation), continue (meth) purified by distillation an acrylic acid ester IV ( Rectification)
At that time, the method for producing (meth) acrylic acid ester IV is characterized in that the catalyst separation is carried out at 125 to 160 ° C. ^{3. The} alcohol according to claim ^{2, wherein the} alcohol R2OH is selected from dimethylaminoethanol, diethylaminoethanol and di-n-butylaminoethanol, 3-dimethylaminopropanol, 3-diethylaminopropanol and 3-di-n-butylaminopropanol. Method.   4. The process according to claim 1, wherein the separation of the (meth) acrylate I is carried out at from 120 to 160 [deg.] C. 5. The process according to claim 1, wherein the boiling point of the alcohol R ² OH exceeds the boiling point of the alcohol R ¹ OH by 20 ° C. or more. Distillate from one or more towers attached to one or more reactors is
If to be an ester exchange reaction (meth) alcohol component of the acrylic acid ester (R 1 ^O-) is methanolate contains 20-40% by weight methanol, and to be an ester exchange reaction (meth) acrylic If the alcohol component in the ester I (R 1 ^O-) of ethanolate contains ethanol 30 to 65 wt%, any one process of claim 1 to 5.   7. The process as claimed in claim 1, wherein the residue of the catalyst separation is at least partially recycled to the transesterification reaction. 8. The process of claim 1, wherein the residue of the catalyst separation is heated separately or together with the residue of the rectification, at least in part, to 100 to 220 DEG C. in the presence or absence of an acidic or basic catalyst. The method according to claim 1.   9. The process according to claim 8, wherein the distillate removed from the heat treatment and / or the catalytic treatment is returned to the volatile-boiling material separation and / or transesterification reaction.   10. The process according to claim 7, wherein the bottoms discharged from the heat treatment and / or the catalyst treatment are reacted with a high-boiling substance containing a hydroxyl group, and the easily boiled substances distilled off in this case are returned to the transesterification reaction. The method of claim 1. The method according to any one of claims 1 to 10, wherein at least a part of the output from the transesterification reaction is returned to the transesterification reaction from the adiabatic intermediate container. The method of claim 11, wherein the insulated intermediate container is heated. The process according to claim 11 or 12, wherein the adiabatic intermediate vessel is connected to the last reactor of the transesterification reaction and / or to a column attached to this reactor. Using the titanium alcoholate Ti ^(OR _{2) 4} as catalyst, any one process of claim 1 13 or. The titanium alcoholate Ti (OR ² ) ₄ is converted from a lower titanium alcoholate Ti (OR ⁴ ) ₄ [where R ⁴ represents C ₁ -C ₈ -alkyl] to a higher alcohol R ² OH [where R ² is as defined above. And R ² OH and R ⁴ OH are, with respect to their boiling points Kp,
Kp. (R ² OH) ≧ Kp. (R ⁴ OH) + 20 ° C
15. The method of claim 14, wherein Removing the alkanol R ⁴ OH resulting in the transesterification reaction from the transesterification reaction method of claim 15. The reaction mixture obtained contains less than 400ppm of ^R 4 OH, claim 15 or 16 A method according. At least in part, the following stabilizers:
Phenothiazine, 4-methyl-2,6-t-butylphenol, hydroquinone monomethyl ether, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and 4-oxo-2,2,6,6- 18. The process according to any one of the preceding claims, wherein the process is carried out in the presence of at least one tetramethylpiperidine-N-oxyl. R ² is 2- (dimethylamino) ethyl, 2- (di -n- butylamino) ethyl or 2- (diethylamino) ethyl, and ^{R 1} is methyl or ethyl, one of the Claims 1 to 18 Or the method of claim 1.